KR101827523B1 - Hybrid supported metallocene catalyst, method for preparing the same, and process for preparing polyolefin using the same - Google Patents

Abstract

The present invention relates to a hybrid supported metallocene catalyst, a process for preparing the same, and a process for preparing an olefin polymer using the same, wherein the hybrid supported metallocene catalyst comprises an inorganic compound or an organic porous Characterized in that the carrier is supported with two metallocene compounds containing a novel cyclopenta [b] fluorenylsilane transition metal compound, and a process for producing the same and a process for producing an olefin polymer using the hybrid supported metallocene catalyst .

Description

TECHNICAL FIELD The present invention relates to a hybrid supported metallocene catalyst, a method for producing the metallocene catalyst, and a method for preparing the same using the same, and a process for preparing the polyolefin using the same,

The present invention relates to a hybrid supported metallocene catalyst, a process for producing the metallocene catalyst, a process for preparing the olefin polymer using the same, and an olefin polymer produced thereby.

The metallocene catalyst is composed of a combination of a main catalyst mainly composed of a transition metal compound centered on a Group 4 metal and an organometallic compound promoter mainly composed of aluminum or boron. The metallocene catalyst is a homogeneous, single-site catalyst. The molecular weight distribution and chemical compositional distribution of the polyolefin produced are very narrow and homogeneous. Depending on the ligand structure of the metallocene catalyst, stereoregularity, comonomer, Responsiveness and hydrogen responsiveness can be freely controlled.

Especially, in the case of polyethylene, enhanced toughness, strength, and environmental stress cracking resistance (ESCR) are very important. Accordingly, there has been proposed a method of improving the mechanical properties of a high molecular weight resin and the processability in a low molecular weight portion by producing a polyolefin having a bimodal or a broad molecular weight distribution.

Bimodal and polyolefins having a broad molecular weight distribution are polymers containing two kinds of average molecular weights of low molecular weight and high molecular weight, and as a method for synthesizing a polymer having such a molecular weight distribution, two different A method of mixing catalysts or introducing two or more catalysts into one carrier to polymerize them is disclosed.

Conventional methods for controlling the molecular weight distribution of polymers generally involve forming multiple metal complexes using two or more metals in the manufacture of catalysts, and determining the molecular weight distribution by active site manipulation of each metal catalyst component To improve.

However, in the prior art, only the polymerization by mixing two catalysts is suggested, and only the selection of organometallic compounds and the homogeneous catalyst system for controlling the molecular weight distribution and the properties of the polymer, There is a limitation in finding specificity in the preparation of applicable supported catalysts and the like.

U.S. Patent No. 6,444,605 B1

An object of the present invention is to provide a hybrid supported metallocene catalyst prepared by surface-treating an inorganic or organic porous support surface with an ionic compound and a co-catalyst, and simultaneously adding two different metallocene compounds.

It is another object of the present invention to provide a process for preparing the hybrid supported metallocene catalyst.

Another object of the present invention is to provide a method for producing a variety of polyolefin products exhibiting high activity and process stability in a slurry or gaseous olefin polymerization process by applying the hybrid supported metallocene catalyst to a single reactor or multiple reactors have.

The present invention provides a hybrid supported metallocene catalyst having a first metallocene compound and a second metallocene compound carried on a carrier surface-treated with an ionic compound and a promoter.

The present invention also relates to a process for preparing a catalyst, comprising: 1) treating a carrier with an ionic compound and a cocatalyst; And 2) carrying the first metallocene compound and the second metallocene compound simultaneously with the ionic compound of the step 1) and the support surface-treated with the promoter to form a hybrid supported metallocene catalyst; The present invention provides a method for preparing a mixed supported metallocene catalyst.

The present invention also provides a process for preparing an olefin polymer using the above mixed supported metallocene catalyst.

The present invention also provides an olefin polymer produced using the above mixed supported metallocene catalyst.

The hybrid supported metallocene catalyst according to the present invention is characterized in that a heterogeneous metallocene supported catalyst comprising a novel cyclopenta [b] fluorenylsilane transition metal compound in an inorganic or organic porous support surface-treated with an ionic compound and a cocatalyst , And in addition to the conventional method of sequentially adding the catalyst, the mixed supported metallocene catalyst according to the present invention can be obtained by simultaneously adding a first metallocene compound and a second metallocene compound to a surface- The catalysts were very active in the olefin polymerization reaction because of the hybrid supported catalyst. The prepared polymer had excellent particle shape and bulk density. Thus, there is a very economical and useful advantage in producing metallocene polyolefins in commercial slurry or gas phase processes.

The present invention relates to a hybrid supported metallocene catalyst having a first metallocene compound and a second metallocene compound carried on a carrier surface-treated with an ionic compound and a cocatalyst, a process for producing the same, and a process for producing the olefin monomer or olefin System and olefin comonomers thereof, to provide an olefin polymer.

Hereinafter, the features of the present invention will be described in detail.

The ionic compounds usable in the present invention are all commercially available ionic compounds, and new ionic compounds may be used through synthesis according to the metallocene catalyst, the structure of the cocatalyst and the carrier type. A characteristic of a commercialized or synthesizable ionic compound is that the ionic compound has a vapor pressure close to 0 and a polarity at a temperature range of -100 to 300 ° C, and the polarity can be changed depending on the kind of anionic material, Various kinds of ionic materials ranging from polarity to very strong polarity can be employed, and any ionic compound free from impurities can be used in the present invention as long as it does not change the molecular structure of the metallocene catalyst to inactive. The ionic compound used in the present invention is represented by the following formula (1).

[Chemical Formula 1]

X ⁺ Y ^-

Wherein X ⁺ is an imidazolium ion, a pyridinium ion, an ammonium ion, a phosphonium ion, a sulfonium ion, a pyrazolium ion, or a pyrrolidium ion, and X ⁺ is -CN, -OH, -SO ₃ H, -COOH, _{amino, -SiR 11 R 12 R 13 (} R 11 to R ₁₃ are independently selected from (C1-C20) alkyl or (C6-C30) aryl each other), (C1-C20) alkyl and (C1 (C1-C20) alkyl group or (C6-C20) aryl group in which one or more functional groups selected from a substituted or unsubstituted C1-C20 alkoxy group are substituted or unsubstituted; Y ^- is BF ₄ ^- , BCl ₄ ^- , PF ₆ ^- , AlCl ₄ ^- , halogen ^- , CH ₃ CO ₂ ^- , CF ₃ CO ₂ ^- , CH ₃ SO ₄ ^- , (CF ₃ SO ₂ ) N ^- , CH ₃ CH ₂ SO ₄ ^- , CF ₃ SO ₃ ^- , N (CN) ₂ ^- , HCO ₃ ^- SCN ^- , NO ₃ ^- , SbF ₆ ^- , Sb ₂ F ₁₁ ^- , MePhSO ₃ ^- , _{(CF 3 SO 2) 2 N} -, _{(CF 3 SO 2) 3 C} -, ^{_{(OR) 2 PO 2 - (}} R = (C1-C20) ^{_{alkyl), Bu 2 PO 2 -,}} Et 2 PO 2 - , or HSO ₄ ^- a.

The cation (X ^< ^{+ &} gt ^; ) in the above formula (1) is illustrated by the following table.

In the above table, R and R ₁ to R ₃ are (C ₁ -C 20) alkyl groups or (C 6 -C 20) aryl groups, and the alkyl groups and aryl groups are -OH, -SO ₃ H, -COOH, amino, -SiR ₁₁ R ₁₂ Wherein at least one functional group selected from R ₁₃ (wherein R ₁₁ to R ₁₃ are each independently of the other (C 1 -C 20) alkyl or (C 6 -C 30) aryl), (C 1 -C 20) alkyl group and (C 1 -C 20) .

The type of anion (Y ^- ) in the above formula (1) is illustrated by the following table.

Examples of ionic compounds usable in the present invention include 1,3-bis (cyanomethyl) -imidazolium chloride, 1-butyl-3-methylimidazolium chloride, 1-butyl- Butyl-3-methylimidazolium dicyanamide, 1-butyl-3-methylimidazolium hexafluoroantimonate, 1-butyl-3-methylimidazolium hexafluoro Butyl-3-methylimidazolium hydrogensulfate, 1-butyl-3-methylimidazolium methylsulfate, 1-butyl-3-methylimidazolium hydrogensulfate, Imidazolium tetrachloroaluminate, 1-butyl-3-methylimidazolium tetrachloroborate, 1-butyl-3-methylimidazolium thiocyanate, 1-dodecyl-3-methylimidazolium iodide , 1-ethyl-2,3-dimethylimidazolium chloride, 1-ethyl-3-methylimidazolium Ethyl-3-methylimidazolium hexafluorophosphate, 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-hexyl-3-methylimidazolium chloride, 1-butyl-4-methylpyridinium chloride, 1-butyl-4-methylpyridinium tetrafluoroborate, 1-butyl-4-methylpyridinium hexafluorophosphate, benzyldimethyl Tetrabutylammonium chloride, tetrabutylammonium chloride, tetradecylammonium chloride, tetraheptylammonium chloride, tetrakis (decyl) ammonium bromide, tributylmethylammonium chloride, tetrahexylammonium iodide, tetrabutylphosphonium chloride, tetrabutylphosphonium tetrafluoroborate, Butyl-1-methylpyrrolidium chloride, 1-butyl-1-methylpyrrolidium bromide, 1-butyl-1-methylpyrrolidium tetrafluoride 3-methylimidazolium bromide, 1-mesityl-3-methylimidazolium chloride, 1-benzyl-3-methylimidazolium hexafluorophosphate, 1-benzyl- Methylimidazolium bis (trifluoromethylsulfonyl) imide, 1-butyl-3-methylimidazolium dibutyl phosphate, 1- (3-cyanopropyl) -3-methylimidazolium bis 1,3-dimethylimidazolium dimethyl phosphate, and 1-ethyl-2,3-dimethylimidazolium ethylsulfate, and preferably 1,3-bis (cyanomethyl) -Imidazolium chloride, 1-butyl-4-methylpyridinium hexafluorophosphate, benzyldimethyltetradecylammonium chloride, tributylmethylaluminium chloride, tetrabutylphosphinium tetrafluoroborate, 1-butyl- Lithium chloride, 1-butyl-3-methylimidazoli Tetrachloro-aluminate, and the like 1-butyl-4-methylpyridinium chloride Stadium, 1-butyl-4-methylpyridinium tetrafluoroborate Stadium.

The inorganic or organic porous carrier treated with the ionic compound is present in the range of 0.001 to 100 mmol per 1 g of the carrier before treatment, with the remaining -OH groups remaining on the surface.

As the carrier treated with the ionic compound, inorganic or organic materials having pores can be used, and they must have pores and surface areas capable of supporting ionic compounds, metallocenes, and cocatalysts. The surfaces of these carriers may have functional groups having hydrophobic properties or may be surface-treated with various aluminum compounds or halogen compounds. Typical inorganic carriers include silica, alumina, magnesium chloride, magnesium oxide, and other carriers that have been used to support metallocene catalysts. In addition, mesoporous materials such as MCM-41, MCM-48, SBA -15, Asahi Glass H-122, and H121 are available. They have a surface area of 100 m ² / g or more and a pore volume of 0.1 cc / g or more. Clay compounds such as mineral clay, kaolin, talc, mica, montmorillonite and the like can also be used as carriers. As the organic carrier, a substance such as a polysiloxane-based polymer compound, polystyrene gel or beads can be employed. These carrier compounds may be used in their original state or they may be heat-treated at a temperature within a range from 100 to 1000 ° C. to control the amount of hydrophobic functional groups and the like in the carrier pore surface.

The composition of the ionic compound carried on the surface of the carrier is related to the physical and chemical properties of the surface of the carrier such as the pore surface area of the carrier and the amount of the hydroxyl group (OH group) on the surface of the carrier, It is suitable that 0.001 to 50% by weight, particularly 0.1 to 40% by weight, is based on the treated carrier. In addition, the amount of the ionic compound should be increased as the amount of the hydroxy group remaining on the surface of the carrier is larger. If the amount of the ionic compound is less than 0.001% by weight, the treatment effect is insignificant. If the amount exceeds 50% by weight, synergistic effect is not obtained by an excessive amount, resulting in waste of the ionic compound.

The composite supported metallocene catalyst according to the present invention is characterized in that a first metallocene compound represented by the following formula (2) and a second metallocene compound represented by the following formula (3) are added to a carrier surface-treated with the ionic compound represented by the above formula Characterized in that a metallocene compound is mixed and supported.

(2)

Cp'L ¹ M ¹ L ² _m

[Formula 2]

M ¹ is a Group 4 transition metal on the periodic table;

Cp 'is a central metal M ¹ and η ⁵ - cycloalkyl which may be bonded cyclopentadienyl or cyclopentadienyl fused ring and comprising a ring;

L ¹ is an anionic ligand containing a fused ring or (C1-C20) hydrocarbon substituent comprising a cyclopentadiene, cyclopentadienyl ring and an O, N or P atom;

L ² represents a halogen atom, a (C 1 -C 20) alkyl group, a (C 6 -C 30) aryl (C 6 -C 20) alkyl group, a (C 3 -C 20) cycloalkyl group, , A (C6-C30) aryl group, -SiR ^a R ^b R ^c , -NR ^d R ^e , -OSiR ^f R ^g R ^h or -PR ⁱ R ^j ;

R ^a to R ^j are independently of each other a (C1-C20) alkyl group or a (C6-C30) aryl group;

m is an integer of 1 or 2;

Wherein Cp 'and L ¹ are not connected to each other or may be connected by a silicon or (C 1 -C 4) alkenylene bond, and the cyclopentadienyl ring or the cyclopentadienyl ring of Cp' and L ¹ The fused ring may be optionally substituted with one or more substituents selected from a (C1-C20) alkyl group, a (C3-C20) cycloalkyl group, a (C6-C30) aryl group, a (C2- More can be substituted.]

(3)

[Wherein M ² is a transition metal of Group 4 in the periodic table;

n is an integer of 1 or 2, and when n is 2, R < ₁ > may be the same or different;

R ₁ is hydrogen, (C1-C20) alkyl, halo (C1-C20) alkyl, (C3-C20) cycloalkyl, (C1-C20) alkyl (C6-C30) aryl, (C6-C30) aryl, (C6 (C 1 -C 20) alkyl, (C 1 -C 20) alkyl, (C 1 -C 20) alkyl (C 6 -C 30) aryl, (C 1 -C 20) alkyl, -NR ^k R ¹ , -SiR ^m R ⁿ R ^o, Lt; RTI ID = 0.0 > N-heterocycloalkyl < / RTI >

R ₂ And R ₃ are independently of each other hydrogen, (C 1 -C 20) alkyl, (C 1 -C 20) alkoxy, halo (C 1 -C 20) alkyl, (C 3 -C 20) cycloalkyl, (C6-C30) aryl, (C6-C30) aryloxy, (C1-C20) alkyl (C6-C30) aryl) (C1-C20) alkyl, -NR ^k R ^l Or -SiR ^m R ⁿ and R ^o;

R ₄ , R ₅ , R ₁₀ , R ₁₁ And R ₁₂ are independently selected from the group consisting of (C 1 -C 20) alkyl, halo (C 1 -C 20) alkyl, (C 3 -C 20) cycloalkyl, (C 1 -C 20) (C1-C20) alkoxy (C6-C30) aryl, (C6-C30) aralkyl (C1-C20) alkyl, ((C1-C20) alkyl (C6-C30) aryl) (C1-C20) alkyl, -NR ^k R ¹ or -SiR ^m R ⁿ R ^o ;

R ₆ , R ₇ , R ₈ And R ₉ are independently of each other hydrogen, (C 1 -C 20) alkyl, halo (C 1 -C 20) alkyl, (C 3 -C 20) cycloalkyl, (C 1 -C 20) alkoxy, (C1-C60) alkyl, (C6-C30) aryl, (C6-C30) C6-C30) aryl, (C6-C30) aryloxy, (C1-C20) alkyl (C6-C30) aryloxy, N- carbazolyl, -NR ^k R ^l Or -SiR ^m R ⁿ or R ^o, an adjacent substituent via (C1-C5) alkyl are alkylene linked to can form a ring, at least one of the alkylene CH ₂ - is -O-, -S-, and NR ' -, wherein said alkylene may be further substituted with (C1-C20) alkyl;

R 'and R ^k To R ^o are, independently of each other, (C1-C20) alkyl or (C6-C30) aryl;

X ₁ and X ₂ are independently of each other selected from the group consisting of halogen, (C 1 -C 20) alkyl, (C ₂ -C 20) alkenyl, (C 3 -C 20) cycloalkyl, (C 6 -C 30) aryl, (C 1 -C 20) alkyl, (C 1 -C 20) alkyl ((C 1 -C 20) alkyl (C 6 -C 30) aryl) Consisting of up to 60 atoms, including N, P, O, S, Si, halogen, etc., except for aryloxy, (C1-C20) alkoxy (C6-C30) aryloxy, Anion or a double anion ligand, provided that X ₁ Or X ₂ One of which is a double anionic ligand, the other is ignored.]

The second metallocene compound represented by Formula 3 is a new transition metal compound based on cyclopenta [b] fluorenyl] group, and the metal of Group 4 on the periodic table as a central metal is not a heterocycle Cyclopenta [b] fluoren-3-yl, which has a rigid, planar structure and is electronically abundant in nature and has a 9-position substituent that is readily accessible for solubility and performance improvement, (b) fluoren-3-yl] group and a silyl group substituted with an amino group, which is advantageous for obtaining an ethylene polymer of high efficiency and high molecular weight. The supported metallocene catalyst is prepared by carrying the second metallocene compound represented by Formula 3 and the first metallocene compound represented by Formula 2 in a mixed manner And a gong.

The second metallocene compound represented by Formula 3 includes a transition metal compound represented by Formula 4 or 5:

[Chemical Formula 4]

[Chemical Formula 5]

[In the above formulas (4) and (5), M ² , R ₂ To R ₁₂ , X ₁ And X < ₂ > are the same as defined in the above formula (3); R ₂₁ And R ₂₂ are each independently of the other hydrogen, (C 1 -C 20) alkyl, halo (C 1 -C 20) alkyl, (C 3 -C 20) cycloalkyl, (C 1 -C 20) aryl, (C6-C30) aralkyl (C1-C20) alkyl, ((C1-C20) alkyl (C6-C30) aryl) (C1-C20) alkyl, -NR ^k R ^l, R ^m -SiR ⁿ R ^o Or 5- to 7-membered N-heterocycloalkyl containing one or more nitrogen atoms; R ^k to R ^o are, independently of each other, (C 1 -C 20) alkyl or (C 6 -C 30) aryl.

The second metallocene compound of Formula 3 may be selected from compounds of the following structures.

[M ² is Ti, Zr or Hf; X < _{1 >} and X < ₂ >

Specific examples of the first metallocene compound of Formula 2 include bis (cyclopentadienyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dichloride, bis (normal butylcyclopentadienyl) zirconium dichloride, Zirconium dichloride, bis (cyclopentylcyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dichloride, bis (1,3-dimethylcyclopentadienyl) zirconium dichloride, bis (Indenyl) zirconium dichloride, bis (fluorenyl) zirconium dichloride, bis (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride, ethylene-bis (Indenyl) zirconium dichloride, ethylene- [bis (4,5,6,7-tetrahydro-1-indenyl)] zirconium dichloride, dimethylsilyl- Zirconium dichloride, diphenylsilyl-bis (indenyl) zirconium dichloride, isopropyl (cyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilyl (cyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylsilyl (Cyclopentadienyl) zirconium dichloride, (1-methyl-3-cyclopentylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, (cyclopentylcyclopentadienyl) Cyclopentadienyl) zirconium dichloride, (1-ethyl-3-cyclopentylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, (1 -butyl-3-cyclopentylcyclopentadienyl) (cyclopentadienyl) Zirconium dichloride, (cyclopentylcyclopentadienyl) (cyclomethylcyclopentadienyl) zirconium dichloride, (1-methyl-3-cyclopentylcyclopentadienyl) (pentamethylcyclopentadienyl) zirconium dichloride (1-ethyl-3-cyclopentylcyclopentadienyl) (pentamethylcyclopentadienyl) zirconium dichloride, (1-butyl-3-cyclopentylcyclopentadienyl) (pentamethylcyclopentadienyl) (Cyclopentadienyl) zirconium dichloride, (1-methyl-3-cyclohexylcyclopentadienyl) (pentamethylcyclopentadienyl) zirconium dichloride, (1-butyl-3-cyclohexylcyclopentadienyl) (pentamethylcyclopentadienyl) zirconium dichloride, (1-butyl-3-cyclohexylcyclopentadienyl) Zirconium dichloride, (cyclohexylmethylenylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, (cycloheptylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, (1-methyl- Heptylcyclopentadienyl) (pentamer (1-butyl-3-cycloheptylcyclopentadienyl) zirconium dichloride, (1-ethyl-3-cycloheptylcyclopentadienyl) (pentamethylcyclopentadienyl) zirconium dichloride, (Pentamethylcyclopentadienyl) zirconium dichloride, (cyclohexylethylenecyclopentadienyl) (cyclopentadienyl) zirconium dichloride, and the like.

The hybrid supported metallocene catalyst according to the present invention may further comprise an alkylaluminoxane cocatalyst, an organoaluminum cocatalyst or a boron compound cocatalyst, or a mixture thereof.

The cocatalyst to be used in the present invention, that is, the cocatalyst which can be further contained in the cocatalyst or mixed supported metallocene catalyst to be treated on the surface of the carrier may be the same or different, and specifically includes an alkyl Aluminoxane, organoaluminum represented by the following general formula (7), and boron compounds represented by the following general formulas (8) to (10).

[Chemical Formula 6]

(-Al (R ³¹ ) -O-) _a

(7)

(R ³² ) _b Al (E) _3-b

[Wherein R ³¹ and R ³² are independently of each other a (C 1 -C 20) alkyl group; E is a hydrogen atom or a halogen atom, a is an integer of 5 to 20; and b is an integer of 1 to 3.]

[Chemical Formula 8]

B (R < ^{41 >} ) ₃

[Chemical Formula 9]

[R ⁴² ] ⁺ [B (R ⁴¹ ) ₄ ] ^-

[Chemical formula 10]

[(R ⁴³ ) _q ZH] ⁺ [B (R ⁴¹ ) ₄ ] ^-

[In the above Chemical Formulas 6 to 8, B is a boron atom; R ⁴¹ is phenyl and said phenyl is optionally substituted with one to three substituents selected from the group consisting of a fluorine atom, (C 1 -C 4) alkyl optionally substituted by fluorine atom, or (C 1 -C 4) alkoxy optionally substituted by fluorine atom Lt; / RTI > may be further substituted with a substituent; R ⁴² is a (C 5 -C 7) cycloalkyl radical, a (C 6 -C 20) aryl radical or a (C 6 -C 20) alkyl radical, For example triphenylmethylium radical; Z is nitrogen or phosphorus; R ⁴³ is a (C ₁ -C ₄ ) alkyl radical or an Anilinium radical substituted with two (C ₁ -C ₄ ) alkyl groups together with the nitrogen atom; q is an integer of 2 or 3.]

Examples of the alkylaluminum compound which can be used include trialkylaluminum including trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tributylaluminum, triisobutylaluminum, triisopentylaluminum and the like; Dialkyl aluminum chlorides including dimethyl aluminum chloride, diethyl aluminum chloride, dipropyl aluminum chloride, diisobutyl aluminum chloride, and dihexyl aluminum chloride; Methylaluminum dichloride, ethylaluminum dichloride, propylaluminum chloride, isobutylaluminum chloride and the like, and the like, preferably trialkylaluminum chloride and triisobutylaluminum chloride.

Preferable examples of the above-mentioned alkylaluminoxane cocatalyst include methylaluminoxane, ethylaluminoxane, propylaluminoxane, butylaluminoxane, isobutylaluminoxane and the like. Preferred examples of the organoaluminum co-catalyst include trimethylaluminum, triethylaluminum, Triethylaluminum chloride, diethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminum chloride, dihexyl aluminum chloride, methyl aluminum < RTI ID = 0.0 > Preferred examples of the boron compound promoter include tris (pentafluorophenyl) borane, tris (2,3,5,6-tetra (pentafluorophenyl) borane, Fluorophenyl) borane , Tris (2,3,4,5-tetrafluorophenyl) borane, tris (3,4,5-trifluorophenyl) borane, tris (2,3,4-trifluorophenyl) (Pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate, tetrakis (2,3,5,6-tetrafluorophenyl) borate, tetrakis (Tetrafluorophenyl) borate, tetrakis (3,4,5-tetrafluorophenyl) borate, tetrakis (2,2,4-trifluorophenyl) borate, phenylbis (pentafluorophenyl) Tetrakis (3,5-bistrifluoromethylphenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenylmethylium tetra (pentafluorophenyl) borate ) borate).

The present invention relates to a process for the preparation of 1) a process for treating a carrier with an ionic compound and a cocatalyst; And 2) carrying a mixture of a first metallocene compound and a second metallocene compound simultaneously on the carrier treated with the ionic compound and co-catalyst in the step 1) to prepare a hybrid supported metallocene catalyst And a method for producing the mixed supported metallocene catalyst.

Hereinafter, a method of preparing the hybrid supported metallocene catalyst according to the present invention will be described.

An inert gas such as nitrogen or argon is flowed at 100 to 900 ° C or treated with a vacuum to adjust the amount of a hydroxyl group on the surface of the inorganic carrier such as silica to be supported. The amount of hydroxyl groups remaining on the surface is preferably 0.001 to 100 mmol-OH / g-silica, and 0.1 to 5 mmol-OH / g-silica is preferable. The above condition is a condition of the carrier before the surface is functionalized with an ionic compound. The required amount of the ionic compound is added to the flask in which the silica prepared in the carrier is packed. The amount of the ionic compound to be added is preferably similar to or higher than the amount of OH groups on the surface of the silica.

The silica and the ionic compound are thoroughly mixed for at least 1 hour in a nitrogen atmosphere at a temperature equal to or higher than the melting point of the ionic compound so that the ionic compound sufficiently contacts the surface of the silica and the hydroxyl group on the surface. Subsequently, the co-catalyst, preferably methylaluminoxane (MAO), is diluted in an organic solvent such as toluene, and the resulting mixture is put into a flask containing silica pretreated with an ionic compound and sufficiently mixed for a suitable time in a nitrogen atmosphere at a suitable temperature. Thereafter, the mixed metallocene compound is dissolved in the co-catalyst and the organic solvent at a suitable temperature, and the mixture is put into the silica surface-treated with the ionic compound and the co-catalyst, and stirred for a suitable time in the nitrogen atmosphere to carry the mixed metallocene. In this case, the molar ratio of the transition metal M to the aluminum atom is preferably 1: 0.1 to 1: 3000, and more preferably 1: 1 to 1: 500. Subsequently, for the removal of the unsupported metallocene and the cocatalyst, an organic solvent such as hexane is used for washing three times or more, followed by drying with a vacuum or a nitrogen gas, and finally a surface treatment with an ionic compound and a promoter Thereby obtaining a hybrid supported metallocene catalyst supported on the carrier.

The transition metal content in the hybrid supported metallocene catalyst produced by the above method was analyzed to be 0.05 to 1.5 wt%.

The mixed supported metallocene catalyst supported on the inorganic or organic porous carrier treated with the ionic compound thus obtained and the co-catalyst can be subjected to single polymerization using one kind of olefin monomer or multi-polymerization using two or more kinds of these monomers, Is subjected to a polymerization reaction in a slurry or gas phase of an organic solvent such as hexane. The hybrid supported metallocene catalyst according to the present invention is dispersed in a reaction solvent in the absence of water. The polymerization reaction solvent is generally an aliphatic hydrocarbon or a mixture thereof. Examples thereof include propane, isobutane, isopentane, hexane , Heptane, octane, and the like.

The mixed supported metallocene catalysts of the present invention are applicable not only to gas phase, slurry, and liquid phase polymerization processes but also to batch and continuous polymerization processes, but they are most suitable for slurry and gas phase reaction.

The batch slurry polymerization process as an example of the polyolefin polymerization process using the hybrid supported metallocene catalyst according to the present invention will be described as follows.

First, water and air are removed from the high-pressure reactor in a vacuum at a high temperature, and then the solvent is charged into the reactor. After the temperature is raised to the polymerization temperature, alkyl aluminum or MAO is added as a scavenger and the mixed supported metallocene The catalyst is introduced. Then, olefins such as ethylene are introduced, and hydrogen is injected as necessary when olefins are added. When the required polymerization time is reached, the addition of olefins is stopped, the unreacted olefin and solvent are removed, and the reactor is opened to obtain a solid polymer.

The polymerization solvent used is a solution of 5 Å molecular sieve and a pipe filled with activated alumina and bubbled with high purity nitrogen to sufficiently remove water, oxygen and other catalyst poisoning substances. The polymerization temperature is -50 to 200 ° C. And 50 to 100 DEG C is suitable. The polymerization pressure is 1 to 50 atm, preferably 5 to 30 atm.

The present invention features a process for preparing an olefin polymer using the above-described hybrid supported metallocene catalyst, wherein the olefin polymer comprises homopolymers or copolymers of alpha olefins.

Examples of possible olefinic monomers that can be employed in the production process according to the present invention include ethylene, alpha olefins, cycloolefins, and diene monomers, triene, styrene, and cyclic olefins.

Examples of such monomers include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, Butene, styrene, alpha-methylstyrene, allylbenzene, divinylbenzene, vinylcyclohexane, vinylcycloheptane, vinylcyclohexane, Cyclopentene, cyclopentene, cycloheptene, norbornene, tetracyclododecene, isoprene, 1,3-butadiene, 1,4-pentadiene, 1,4-hexadiene and cyclopentadiene. Two or more of them may be mixed and polymerized.

Hereinafter, the present invention will be described by way of Comparative Examples and Examples, but the present invention is not limited by the following Examples.

The hybrid supported metallocene catalyst and the polymer polymer analysis according to the present invention were carried out in the following manner.

1) the metal content in the supported catalyst

The metal content was measured by ICP analysis.

2) Melt index

It was measured according to ASTM D 2839.

3) Melting point analysis

Using Dupont DSC2910 was measured at 2 ^nd heating condition to 20 ℃ / min. Rate under cant atmosphere.

4) Molecular weight and molecular weight distribution

TOHO Company Column TSK Guard Column HHR (S) + TSK-Gel The PL GPC210 (manufactured by Polymer Laboratories) equipped with GMHHR H (S) was measured at 160 ° C at a rate of 1 ml / min. 1,2,3-trichlorobenzene was used as the solvent, and the molecular weight was corrected by the standard sample PS1_A, B (Mw = 580 to 7,500,000).

[Preparation Example 1] Preparation of second metallocene compound

Preparation of 9,9-dihexyl-9H-fluorene (9,9-dihexyl-9H-fluorene)

Add 9H-fluorene (50 g, 300.1 mmol) and potassium tert-butoxide (77.0 g, 721.9 mmol) to a 2000 mL round-bottomed flask and slowly inject 700 mL of DMSO. 1-Bromohexane (119 g, 721.9 mmol) is added dropping funnel under nitrogen atmosphere and slowly dropped. After stirring for 24 hours at room temperature, 500 mL of distilled water was added to terminate the reaction. The reaction mixture was extracted with n-hexane, and the combined organic layer was dried over magnesium sulfate, and the volatiles were removed. The residue was purified by silica gel chromatography using n-hexane After drying, it was stored at room temperature for an extended period of time to obtain 90.0 g (yield: 72.40%) of solid 9,9-dihexyl-9H-fluorene.

^{1 H-NMR (500MHz, CDCl} 3, ppm): δ = 0.625-0.628 (m, 4H), 0.759-0.785 (m, 6H), 1.050-1.125 (m, 12H), 1.953-1.983 (t, 4H) , 7.293-7.340 (m, 6H), 7.706-7.720 (d, 2H)

Preparation of 9,9-dihexyl-2-methyl-2,3-dihydrocyclopenta [b] fluorene-1 (9H)

In a 2000 mL round flask, 9,9-dihexyl-9H-fluorene (79 g, 236.2 mmol), 2-bromo-2-methylpropanoyl bromide (54.3 g, 236.2 mmol), add 600 mL of carbon disulfide to dissolve it, and cool the reactor with ice water. Aluminum trichloride (78.7 g, 590.4 mmol) is slowly poured in 10 portions over 2 hours under a nitrogen atmosphere. After stirring at room temperature for 8 hours, add 500 mL of distilled water to terminate the reaction, and wash it with 500 mL of distilled water for 3 times. The organic layer was dried with magnesium sulfate, and the volatiles were removed therefrom and then dried to obtain 9,9-dihexyl-2-methyl-2,3-dihydrocyclopenta [b] fluorene-1 (9H) 89.0 g (yield: 93.6%) was obtained.

^{1 H-NMR (500MHz, CDCl} 3, ppm): δ = 0.601-0.627 (m, 4H), 0.741-0.774 (m, 6H), 1.000-1.126 (m, 12H), 1.366-1.380 (d, 3H) 2H), 7.764-7.779 (d, 2H), 1.961-2.202 (m, 4H), 2.789-2.801 (d, 2H), 3.445-3.498 1H)

Production of 9,9-dihexyl-2-methyl-1,2,3,9-tetrahydrocyclopenta [b] fluoren-1-ol

(9H) -one (85 g, 211.1 mmol) was dissolved in 400 mL of THF and 400 mL of ethanol in a 1000 mL round-bottomed flask, and a solution of 9,9-dihexyl-2-methyl-2,3-dihydrocyclopenta [ Then stir. Sodium borohydride (NaBH ₄ ) (10 g, 265.0 mmol) is added in five portions and stirred for 12 hours. After removing all the solvent, dissolve in ethyl acetate and wash 3 times with water. The organic layer was dried with magnesium sulfate, and the volatiles were removed therefrom and then dried to obtain 9-dihexyl-2-methyl-1,2,3,9-tetrahydrocyclopenta [b] fluoren- 82.0 g (yield 96.0%) was obtained (two isomeric forms).

¹ H-NMR (500 MHz, CDCl ₃ , ppm):? = 0.628-0.631 (m, 8H), 0.762-0.788 (m, 12H), 1.109-1.136 (m, 24H), 1.198-1.212 (D, 1H), 1.956-1.963 (m, 8H), 2.323-2.352 (m, 1H), 2.525-2.572 (m, 1H), 2.628-2.655 (m, 1H), 2.733-2.779 (m, 1H), 3.011-3.057 1H), 7.672-7.685 (d, 2H), 7.525 (s, IH)

9,9- Dihexyl -2- methyl -3,9- Dihydrocyclopenta [b] fluorene  Produce

80 g (197.7 mmol) of 9-dihexyl-2-methyl-1,2,3,9-tetrahydrocyclopenta [b] fluorene-1-ol and 0.2 g of paratoluenesulfonic acid were added to a 500 mL round- After dissolving in 320 mL of toluene, Dean-Stark was installed and the water was completely removed by refluxing. After cooling to room temperature, ammonium chloride aqueous solution (150 mL) and 200 mL of diethyl ether were poured into the mixture. The organic layer was separated and the residue was extracted with diethyl ether. The combined organic layer was dried with magnesium sulfate, 74.0 g (yield: 96.8%) of 9,9-dihexyl-2-methyl-3,9-dihydrocyclopenta [b] fluorene was obtained by using a silica gel chromatography tube.

^{1 H-NMR (500MHz, CDCl} 3, ppm): δ = 0.611-0.671 (m, 4H), 0.755-0.784 (m, 6H), 1.041-1.140 (m, 12H), 1.943-1.976 (m, 4H) , 2.200 (s, 3H), 3.373 (s, 2H), 6.556 (s, IH), 7.208-7.381 (m, 4H), 7.653-7.668

N-tert-butyl-1- (9,9-hexyl-2-methyl-3,9-dihydrocyclopenta [b] fluoren- butyl-1- (9,9-dihexyl-2-methyl-3,9-dihydrocyclopenta [b] fluoren- (9,9-dihexyl-2-methyl-1,9-dihydrocyclopenta [b] fluorene- methyl-1,9-dihydrocyclopenta [b] fluoren-1-yl) -1,1-dimethylsilanamine

Dioxyl-2-methyl-3,9-dihydrocyclopenta [b] fluorene (40.0 g, 103.5 mmol) was dissolved in 320 mL of diethyl ether in a 500 mL round- , And then N-butyllithium (2.5 M hexane solution, 42 mL) was slowly added thereto, followed by stirring at room temperature for 12 hours. After removing the volatiles by vacuum, 350 mL of n-hexane was added, the reactor temperature was lowered to -78 ° C, and dichlorodimethylsilane (40 g) was added. The temperature was raised to room temperature again, and the mixture was stirred for 24 hours. Then, the salt was removed by filtration. And removes volatiles by vacuum. The product was put into a 500 mL round-bottomed flask, and dissolved in 320 mL of diethyl ether. After the temperature was lowered to -78 ° C, tert-butylamine (22.7 g, 310.4 mmol) was added. The temperature is raised to room temperature and stirred for 12 hours, then the volatiles are completely removed in vacuo. Add 200 mL of n-hexane to dissolve and remove the salt by filtration. Removal of the solvent gave N-tert-butyl-1- (9,9-hexyl-2-methyl-3,9-dihydrocyclopenta [b] fluoren- A mixture of silane amine and N-tert-butyl-1- (9,9-hexyl-2-methyl-1,9-dihydrocyclopenta [b] fluoren- (Yield: 88.9%) of the title compound (ratio = ~ 1: 1).

¹ H-NMR (500 MHz, C ₆ D ₆ , ppm):? = 0.132 (s, 3H), 0.177-0.198 (d, 6H), 0.270 (s, 1H), 0.804-0.879 2H), 7.337-7.434 (m, 6H), 7.518-7.908 (m, 6H)

(t-butylamido) dimethyl (9,9-hexyl-2-methyl-3,9-dihydrocyclopenta [b] fluoren-3-yl) silane titanium (IV) dimethyl -Butylamido) dimethyl (9,9-hexyl-2-methyl-1,9-dihydrocyclopenta [b] fluoren-1-yl) silane titanium (IV) dimethyl

A mixture of 250 ml N-tert-butyl-1- (9,9-hexyl-2-methyl-3,9-dihydrocyclopenta [b] fluoren- a mixture of tert-butyl-1- (9,9-hexyl-2-methyl-1,9-dihydrocyclopenta [b] fluoren- : 1) (8.64 g, 16.75 mmol) was dissolved in 130 mL of diethyl ether, the temperature was lowered to -78 ° C., and methyl lithium (1.5 M diethyl ether solution, 49.4 mL) was slowly added. The temperature is raised to room temperature and stirred for 12 hours to form a lithium salt. Then, in a 500 mL round flask in a dry box, TiCl ₄ (16.75 mmol) and 150 mL of anhydrous n-hexane are added, the temperature is lowered to -78 ° C, and the previously prepared lithium salt is added slowly. The temperature was raised to room temperature again and stirred for 4 hours. Then, the solvent was removed by vacuum, dissolved in n-hexane, and filtered to extract the filtrate. The pentane was again removed by vacuum to obtain 8.1 g of a mixture of complex 1 and complex 2 (in a ratio of almost 1: 1).

^{1 H-NMR (500MHz, C} 6 D 6, ppm): δ = 0.079-0.091 (d, 6H), 0.623-0.645 (d, 6H), 0.813-1.336 (m, 56H), 1.601-1.619 (d, 18H), 2.071-2.514 (m, 14H), 7.025-7.035 (d, 2H), 7.330-8.099 (m, 12H)

[Comparative Preparation Example 1] Preparation of a second metallocene compound: (t-butylamido) dimethyl (tetramethylcyclopentadienyl) silane titanium (IV) dimethyl

(t-butylamido) dimethyl (tetramethylcyclopentadienyl) silane titanium (IV) dimethyl compound is commercially available from Boulder Scientific, (IV) dichloride was dissolved in diethyl ether and cooled to -78 ° C and reacted with 2 equivalents of methyllithium.

[ Example  One]

1. Ionic compounds and As co-catalyst  Hybrid to surface treated silica Metallocene Bearing  Catalyst preparation

A round bottom flask containing silica H-122 (Japan, ASAI GLASS, average particle size 12 u m, surface area 700 m ² / g, average pore volume 1.8 ml / g, average pore diameter 20 nm) , 18.3 mg (0.1 mmol) of 3-bis (cyanomethyl) -imidazolium chloride (Fluka) was added thereto and 50 mmol-Al of MAO (aluminum content 7 wt% Respectively. And sufficiently stirred at 100 占 폚 for 3 hours using a magnetic bar. After the temperature was lowered to 80 캜, 64.7 mg (0.16 mmol) of bis (n-butylcyclopentadienyl) zirconium dichloride ((n-BuCp) ₂ ZrCl ₂ , Boulder Co.) as a first metallocene catalyst, (9,9-hexyl-2-methyl-3 (1), 9-dihydrocyclopenta [b] fluoro-3 (1) -nyl) silane titanium ( IV) Dimethyl (Preparation Example 1) (142 mg, 0.24 mmol) were simultaneously added thereto, followed by stirring at 70 ° C for 3 hours to carry the mixed metallocene and MAO. After stirring was stopped, the unreacted MAO and the metallocene were removed by filtration, followed by vacuum drying. The resultant mixed supported metallocene catalyst was 3.4 g.

2. Ethylene slurry polymerization

1.9 L of hexane was added to a 3 L high-pressure reactor which had been washed in a high-temperature vacuum, and then the temperature was raised to 70 ° C. Then, 1 mmol-Al of triethylaluminum (TEAL) was added thereto and 20 mg of the hybrid supported metallocene catalyst prepared in the above step Hexane slurry into the reactor. The ethylene pressure was adjusted so that the total pressure in the reactor was 8 atm. After the ethylene gas was supplied to saturate it, the ethylene polymerization reaction was started by rotating the stirrer. The total polymerization reaction time was 60 minutes and the temperature was maintained at 80 ° C. After completion of the reaction, the resulting polymer was washed with ethanol and dried in vacuo to obtain 137 g of a polymer.

[ Example  2]

1. Ionic compounds and As co-catalyst  Hybrid to surface treated silica Metallocene Bearing  Catalyst preparation

(T-butylamido) dimethyl (2,9,9-trimethyl-3, 9-dihydroxybenzoyl) was used as a second metallocene compound in comparison with the hybrid supported metallocene catalyst production process of 1. in [Example 1] Dihydrocyclopenta [b] fluoro-3-yl) silane titanium (IV) dimethyl was used as the catalyst. The obtained supported catalyst was 3.34 g.

2. Ethylene Slurry  polymerization

Using the supported catalyst prepared in the above step, a polymerization reaction was carried out in the same manner as in the polymerization of the ethylene slurry in 2 of [Example 1] to obtain 133 g of a polymer.

[Example 3]

1. Preparation of catalyst carrying hybrid metallocene on silica surface-treated with ionic compound and cocatalyst

Compared with the hybrid supported metallocene catalyst production process of [Example 1], the (meth) (Dihydrocyclopenta [b] fluoro-3-yl) silane titanium (IV) dimethyl was used in place of 111.7 mg (0.24 mmol) of the obtained supported catalyst.

2. Ethylene slurry polymerization

Using the supported catalyst prepared in the above step, a polymerization reaction was carried out in the same manner as in the polymerization of the ethylene slurry in 2 of [Example 1] to obtain 129 g of a polymer.

[Comparative Example 1]

1. Preparation of catalyst carrying hybrid metallocene on silica surface-treated with ionic compound and cocatalyst

(T-butylamido) dimethyl (tetramethylcyclopentadienyl) silane titanium (IV) dimethyl (meth) acrylate as a second metallocene compound in comparison with the hybrid supported metallocene catalyst preparation process of [Example 1] Except that 78.6 mg (0.24 mmol) of Comparative Preparation Example 1 was used. The obtained supported catalyst was 3.23 g.

2. Ethylene slurry polymerization

Using the supported catalyst prepared in the above step, a polymerization reaction was carried out in the same manner as in the polymerization of the ethylene slurry in 2 of [Example 1] to obtain 95 g of a polymer.

** Catalyst Synthesis carrier
(g) Ionic
Compound ^{1 )} MAO (7 wt%) Metallocene input
(mmol) input
(mmol) Treatment temperature
(° C) process
time
(hr) The first metallocene The second metallocene Treatment temperature
(° C) Processing time
(hr) Kinds input
(mmol) Kinds input
(mmol) Example One One 0.1 35.8 100 3 A ²⁾ 0.16 B ³⁾ 0.24 80 3 2 One 0.1 35.8 100 3 A 0.16 C ^{4 )} 0.24 80 3 3 One 0.1 35.8 100 3 A 0.16 D ^{5 )} 0.24 80 3 Comparative Example One One 0.1 35.8 100 3 A 0.16 E ^{6 )} 0.24 80 3 1) 1,3-bis (cyanomethyl) -imidazolium chloride 2) A: Bis (n-butylcyclopentadienyl) zirconium dichloride
3) B: Synthesis of titanium (9,9-hexyl-2-methyl-3 (1), 9-dihydrocyclopenta [b] fluoro-3 (1) IV) Dimethyl
4) C: (t-butylamido) dimethyl (2,9,9-trimethyl-3,9-dihydrocyclopenta [b]
5) D: Dimethyl (1,2,9,9-tetramethyl-3,9-dihydrocyclopenta [b] fluoro-3-yl) silane Titanium (IV) dimethyl
6) E: (t-butylamido) dimethyl (tetramethylcyclopentadienyl) silane titanium (IV) dimethyl

** Polymerization conditions and results Upon polymerization
Co-catalyst menstruum Amount of catalyst
(mg) PE yield
(g) activation MI GPC
MWD DSC
(° C) Bulk
Density Example One TEAL n-hexane 20 137 7.0 0.58 2.36 123.87 0.33 2 TEAL n-hexane 20 133 6.7 0.77 2.14 124.47 0.35 3 TEAL n-hexane 20 129 6.5 0.75 2.56 124.04 0.35 Comparative Example One TEAL n-hexane 20 95 4.8 0.52 2.37 125.04 0.33 * Activity: kg-PE / g-cat., 1 hr, 8 bar * MI: g / 10 min.
Polymerization pressure and time: 8 bar, 60 min. Bulk Density: g / cc

Claims (16)

Characterized in that a first metallocene compound represented by the following formula (2) and a second metallocene compound represented by the following formula (3) are mixed and supported on a carrier surface-treated with an ionic compound represented by the following formula (1) A metallocene catalyst.
[Chemical Formula 1]
X ⁺ Y ^-
Wherein X ⁺ is an imidazolium ion, a pyridinium ion, an ammonium ion, a phosphonium ion, a sulfonium ion, a pyrazolium ion, or a pyrrolidium ion, and X ⁺ is -CN, -OH, -SO ₃ H, -COOH, _{amino, -SiR 11 R 12 R 13 (} R 11 to R ₁₃ are independently selected from (C1-C20) alkyl or (C6-C30) aryl each other), (C1-C20) alkyl and (C1 (C1-C20) alkyl group or (C6-C20) aryl group in which one or more functional groups selected from a substituted or unsubstituted C1-C20 alkoxy group are substituted or unsubstituted; Y ^- is BF ₄ ^- , BCl ₄ ^- , PF ₆ ^- , AlCl ₄ ^- , halogen ^- , CH ₃ CO ₂ ^- , CF ₃ CO ₂ ^- , CH ₃ SO ₄ ^- , (CF ₃ SO ₂ ) N ^- , CH ₃ CH ₂ SO ₄ ^- , CF ₃ SO ₃ ^- , N (CN) ₂ ^- , HCO ₃ ^- SCN ^- , NO ₃ ^- , SbF ₆ ^- , Sb ₂ F ₁₁ ^- , MePhSO ₃ ^- , _{(CF 3 SO 2) 2 N} -, _{(CF 3 SO 2) 3 C} -, ^{_{(OR) 2 PO 2 - (}} R = (C1-C20) ^{_{alkyl), Bu 2 PO 2 -,}} Et 2 PO 2 - , or HSO ₄ ^- a.
(2)
Cp'L ¹ M ¹ L ² _m
[Formula 2]
M ¹ is a Group 4 transition metal on the periodic table;
Cp 'is a central metal M ¹ and η ⁵ - cycloalkyl which may be bonded cyclopentadienyl or cyclopentadienyl fused ring and comprising a ring;
L ¹ is an anionic ligand containing a fused ring or (C1-C20) hydrocarbon substituent comprising a cyclopentadiene, cyclopentadienyl ring and an O, N or P atom;
L ² represents a halogen atom, a (C 1 -C 20) alkyl group, a (C 6 -C 30) aryl (C 6 -C 20) alkyl group, a (C 3 -C 20) cycloalkyl group, , A (C6-C30) aryl group, -SiR ^a R ^b R ^c , -NR ^d R ^e , -OSiR ^f R ^g R ^h or -PR ⁱ R ^j ;
R ^a to R ^j are independently of each other a (C1-C20) alkyl group or a (C6-C30) aryl group;
m is an integer of 1 or 2;
Wherein Cp 'and L ¹ are not connected to each other or may be connected by a silicon or (C 1 -C 4) alkenylene bond, and the cyclopentadienyl ring or the cyclopentadienyl ring of Cp' and L ¹ The fused ring may be optionally substituted with one or more substituents selected from a (C1-C20) alkyl group, a (C3-C20) cycloalkyl group, a (C6-C30) aryl group, a (C2- More can be substituted.]
(3)

[Wherein M ² is a transition metal of Group 4 in the periodic table;
n is an integer of 1 or 2, and when n is 2, R < ₁ > may be the same or different;
R ₁ is hydrogen, (C1-C20) alkyl, halo (C1-C20) alkyl, (C3-C20) cycloalkyl, (C1-C20) alkyl (C6-C30) aryl, (C6-C30) aryl, (C6 -C30) are (C1-C20) alkyl, ((C1-C20) alkyl (C6-C30) aryl) (C1-C20) alkyl, -NR ^k R ^l, R ^m -SiR ⁿ R ^o Or 5- to 7-membered N-heterocycloalkyl containing one or more nitrogen atoms;
R ₂ And R ₃ are independently of each other hydrogen, (C 1 -C 20) alkyl, (C 1 -C 20) alkoxy, halo (C 1 -C 20) alkyl, (C 3 -C 20) cycloalkyl, (C6-C30) aryl, (C6-C30) aryloxy, (C1-C20) alkyl (C6-C30) aryl) (C1-C20) alkyl, -NR ^k R ^l Or -SiR ^m R ⁿ and R ^o;
R ₄ , R ₅ , R ₁₀ , R ₁₁ And R ₁₂ are independently selected from the group consisting of (C 1 -C 20) alkyl, halo (C 1 -C 20) alkyl, (C 3 -C 20) cycloalkyl, (C 1 -C 20) (C1-C20) alkoxy (C6-C30) aryl, (C6-C30) aralkyl (C1-C20) alkyl, ((C1-C20) alkyl (C6-C30) aryl) (C1-C20) alkyl, -NR ^k R ^l Or -SiR ^m R ⁿ and R ^o;
R ₆ , R ₇ , R ₈ And R ₉ are independently of each other hydrogen, (C 1 -C 20) alkyl, halo (C 1 -C 20) alkyl, (C 3 -C 20) cycloalkyl, (C 1 -C 20) alkoxy, (C1-C60) alkyl, (C6-C30) aryl, (C6-C30) C6-C30) aryl, (C6-C30) aryloxy, (C1-C20) alkyl (C6-C30) aryloxy, N- carbazolyl, -NR ^k R ^l or R ^m -SiR ⁿ R ^o, or, adjacent substituent and (C1-C5) can be connected by an alkylene to form a ring, at least one CH ₂ of the alkylene- may be substituted by a heteroatom selected from -O-, -S- and NR'-, the Alkylene may be further substituted with (C1-C20) alkyl;
R 'and R ^k To R ^o are, independently of each other, (C1-C20) alkyl or (C6-C30) aryl;
X ₁ and X ₂ are independently of each other selected from the group consisting of halogen, (C 1 -C 20) alkyl, (C ₂ -C 20) alkenyl, (C 3 -C 20) cycloalkyl, (C 6 -C 30) aryl, (C 1 -C 20) alkyl, (C 1 -C 20) alkyl ((C 1 -C 20) alkyl (C 6 -C 30) aryl) Anion consisting of up to 60 atoms including N, P, O, S, Si, halogen except hydrogen, (C1-C60) aryloxy, (C1- C20) alkoxy Or a double anion ligand, provided that X ₁ Or X ₂ One of which is a double anionic ligand, the other is ignored.]
The method according to claim 1,
Wherein the ionic compound is polar in liquid or solid phase in a temperature range of -100 to 300 占 폚.
3. The method of claim 2,
The ionic compound is selected from the group consisting of 1,3-bis (cyanomethyl) -imidazolium chloride, 1-butyl-3-methylimidazolium chloride, 3-methylimidazolium dicyanamide, 1-butyl-3-methylimidazolium hexafluoroantimonate, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-butyl- Butyl-3-methylimidazolium methylsulfate, 1-butyl-3-methylimidazolium tetrachloroaluminate, 1-butyl-3-methylimidazolium hydrogen sulfate, 1-butyl-3-methylimidazolium thiocyanate, 1-dodecyl-3-methylimidazolium iodide, 1-ethyl- Dimethylimidazolium chloride, 1-ethyl-3-methylimidazolium bromide, 1-ethyl-3-methylimidazole Ethyl-3-methylimidazolium tetrafluoroborate, 1-hexyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium hexafluorophosphate, Butyl-4-methylpyridinium chloride, 1-butyl-4-methylpyridinium tetrafluoroborate, 1-butyl-4-methylpyridinium hexafluorophosphate, benzyldimethyltetradecylammonium chloride, tetraheptylammonium chloride, tetra Tetrabutylphosphonium bromide, tributylmethylammonium chloride, tetrahexylammonium iodide, tetrabutylphosphonium chloride, tetrabutylphosphonium tetrafluoroborate, triisobutylmethylphosphonium tosylate, 1-butyl-1- Butyl-1-methylpyrrolidium bromide, 1-butyl-1-methylpyrrolidium tetrafluoroborate, 1-mesityl-3-methyl imide Methylimidazolium hexafluorophosphate, 1-benzyl-3-methylimidazolium bis (trifluoromethylsulfonyl) bis (trifluoromethylsulfonyl) Imidazolium dibutyl phosphate, 1- (3-cyanopropyl) -3-methylimidazolium bis (trifluroromethylsulfonyl) amide, 1,3-dimethyl Wherein the metallocene catalyst is at least one selected from the group consisting of imidazolium dimethylphosphate and 1-ethyl-2,3-dimethylimidazolium ethylsulfate.
The method according to claim 1,
Wherein the second metallocene compound represented by the general formula (3) is represented by the following general formula (4) or (5).
[Chemical Formula 4]

[Chemical Formula 5]

[Wherein M ² , R ₂ to R ₁₂ , X ₁ and X ₂ are the same as defined in Formula 3 of Claim 1; R ₂₁ and R ₂₂ are independently from each other hydrogen, (C 1 -C 20) alkyl, halo (C 1 -C 20) alkyl, (C 3 -C 20) cycloalkyl, (C 1 -C 20) C30) aryl, (C6-C30) aralkyl (C1-C20) alkyl, ((C1-C20) alkyl (C6-C30) aryl) (C1-C20) alkyl, -NR ^k R ^{l, m} -SiR ⁿ R R ^o or 5 to 7 membered N-heterocycloalkyl containing at least one nitrogen atom; R ^k to R ^o are, independently of each other, (C 1 -C 20) alkyl or (C 6 -C 30) aryl.
The method according to claim 1,
Wherein the cocatalyst is at least one selected from the group consisting of alkylaluminoxanes represented by the following formula (6), organoaluminum represented by the following formula (7), and boron compounds represented by the following formulas (8) to (10).
[Chemical Formula 6]
(-Al (R ³¹ ) -O-) _a
(7)
(R ³² ) _b Al (E) _3-b
[Wherein R ³¹ and R ³² are independently of each other a (C 1 -C 20) alkyl group; E is a hydrogen atom or a halogen atom, a is an integer of 5 to 20; and b is an integer of 1 to 3.]
[Chemical Formula 8]
B (R < ^{41 >} ) ₃
[Chemical Formula 9]
[R ⁴² ] ⁺ [B (R ⁴¹ ) ₄ ] ^-
[Chemical formula 10]
[(R ⁴³ ) _q ZH] ⁺ [B (R ⁴¹ ) ₄ ] ^-
[In the above Chemical Formulas 6 to 8, B is a boron atom; R ⁴¹ is phenyl and said phenyl is optionally substituted with one to three substituents selected from the group consisting of a fluorine atom, (C 1 -C 4) alkyl optionally substituted by fluorine atom, or (C 1 -C 4) alkoxy optionally substituted by fluorine atom Lt; / RTI > may be further substituted with a substituent; R ⁴² is (C5-C7) cycloalkyl radical, (C6-C20) aryl radical, (C1-C20) alkyl (C6-C20) aryl radical or (C6-C30) aralkyl (C1-C20) alkyl radical; Z is nitrogen or phosphorus; R ⁴³ is an (Cl-C4) alkyl radical or an Anilinium radical substituted with two (C1-C4) alkyl groups together with the nitrogen atom; q is an integer of 2 or 3.]
6. The method of claim 5,
Wherein the aluminoxane compound is at least one selected from methyl aluminoxane, ethyl aluminoxane, propyl aluminoxane, butyl aluminoxane, and isobutyl aluminoxane;
Wherein the organoaluminum compound is selected from the group consisting of trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tributylaluminum, triisobutylaluminum, triisopentylaluminum, dimethylaluminum chloride, diethylaluminum chloride, At least one selected from the group consisting of isobutylaluminum chloride, dihexylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, propylaluminum chloride and isobutylaluminum chloride;
Wherein the boron compound is at least one compound selected from the group consisting of tris (pentafluorophenyl) borane, tris (2,3,5,6-tetrafluorophenyl) borane, tris (2,3,4,5-tetrafluorophenyl) (Pentafluorophenyl) borane, tris (3,4,5-trifluorophenyl) borane, tris (2,3,4-trifluorophenyl) ) Borate, tetrakis (2,3,5,6-tetrafluorophenyl) borate, tetrakis (2,3,4,5-tetrafluorophenyl) borate, tetrakis (3,4,5-tetrafluoro (3,5-bistrifluoromethylphenyl) borate, N, N-bis (trifluoromethylphenyl) borate, tetrakis (Triphenylmethylium tetrakis (pentafluorophenyl) borate) and triphenylmethyltrimethylammonium tetrakis (pentafluorophenyl) borate in the presence of a catalyst, 1 kinds of mixed supported metallocene catalyst metal, characterized in that not less than that.
The method according to claim 1,
Wherein the carrier is an inorganic or organic porous carrier selected from silica, alumina, magnesium chloride, magnesium oxide, mineral clay, kaolin, talc, mica, montmorillonite, polysiloxane polymeric compound, polystyrene and mixtures thereof Hybrid supported metallocene catalysts.
The method of claim 3,
Wherein the ionic compound is contained in an amount of 0.001 to 50 wt% based on the surface-treated carrier.
5. The method of claim 4,
Wherein the second metallocene compound represented by Formula 3 is selected from compounds having the following structures.

[M ² is Ti, Zr or Hf; X < _{1 >} and X < ₂ > are the same as defined in formula (3)
The method according to claim 1,
The first metallocene compound represented by the general formula (2) may be at least one selected from the group consisting of bis (cyclopentadienyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dichloride, bis (normal butylcyclopentadienyl) zirconium dichloride, bis (Cyclopentylcyclopentadienyl) zirconium dichloride, bis (cyclohexylcyclopentadienyl) zirconium dichloride, bis (1,3-dimethylcyclopentadienyl) zirconium dichloride, bis (isobutylcyclopentadienyl) ) Zirconium dichloride, bis (indenyl) zirconium dichloride, bis (fluorenyl) zirconium dichloride, bis (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride, ethylene- Zirconium dichloride, ethylene- [bis (4,5,6,7-tetrahydro-1-indenyl)] zirconium dichloride, dimethylsilyl-bis (indenyl) zirconium dichloride, (Cyclopentadienyl) zirconium dichloride, isopropyl (cyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilyl (cyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylsilyl (Cyclopentadienyl) zirconium dichloride, (1-methyl-3-cyclopentylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, (cyclopentylcyclopentadienyl) zirconium dichloride, Zirconium dichloride, (1-ethyl-3-cyclopentylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, (1-butyl-3-cyclopentylcyclopentadienyl) (cyclopentadienyl) zirconium di (Cyclopentylcyclopentadienyl) zirconium dichloride, (1-methyl-3-cyclopentylcyclopentadienyl) (pentamethylcyclopentadienyl) zirconium dichloride, (Pentamethylcyclopentadienyl) zirconium dichloride, (1-butyl-3-cyclopentylcyclopentadienyl) (pentamethylcyclopentadienyl) zirconium di (Cyclopentadienyl) zirconium dichloride, (1-methyl-3-cyclohexylcyclopentadienyl) (pentamethylcyclopentadienyl) zirconium dichloride, (1 (Pentamethylcyclopentadienyl) zirconium dichloride, (1-butyl-3-cyclohexylcyclopentadienyl) (pentamethylcyclopentadienyl) zirconium di (Cyclopentadienyl) zirconium dichloride, (cycloheptylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, (1-methyl-3-cycloheptylcyclopentadienyl) Pentadienyl) (pentamethyl < / RTI > (Pentadienyl) zirconium dichloride, (1-ethyl-3-cycloheptylcyclopentadienyl) (pentamethylcyclopentadienyl) zirconium dichloride, (1 -butyl-3-cycloheptylcyclopentadienyl) (Cyclopentadienyl) zirconium dichloride and (cyclohexylethylenecyclopentadienyl) (cyclopentadienyl) zirconium dichloride. 2. A metallocene catalyst composition as claimed in claim 1, wherein the catalyst is selected from the group consisting of methylcyclopentadienyl) zirconium dichloride and (cyclohexylethylenecyclopentadienyl) (cyclopentadienyl) zirconium dichloride.
The method according to claim 1,
Further comprising at least one cocatalyst selected from the group consisting of an alkylaluminoxane promoter, an organoaluminum promoter, and a boron compound promoter.
1) treating the carrier with an ionic compound and cocatalyst; And
2) a first metallocene compound and a second metallocene compound represented by the following formula (3) are mixed and supported simultaneously on the carrier treated with the ionic compound and the co-catalyst of step 1) to prepare a hybrid supported metallocene catalyst Wherein the metallocene catalyst is supported on a support.
(3)

[Wherein M ² is a transition metal of Group 4 in the periodic table;
n is an integer of 1 or 2, and when n is 2, R < ₁ > may be the same or different;
R ₁ is hydrogen, (C1-C20) alkyl, halo (C1-C20) alkyl, (C3-C20) cycloalkyl, (C1-C20) alkyl (C6-C30) aryl, (C6-C30) aryl, (C6 (C 1 -C 20) alkyl, (C 1 -C 20) alkyl, (C 1 -C 20) alkyl (C 6 -C 30) aryl, (C 1 -C 20) alkyl, -NR ^k R ¹ , -SiR ^m R ⁿ R ^o, Lt; RTI ID = 0.0 > N-heterocycloalkyl < / RTI >
R ₂ and R ₃ are independently of each other hydrogen, (C 1 -C 20) alkyl, (C 1 -C 20) alkoxy, halo (C 1 -C 20) alkyl, (C 3 -C 20) cycloalkyl, (C6-C30) aryl, (C6-C30) aryl, (C6-C30) aryloxy, (C1- C20) alkyl (C6-C30) aryl) (C1-C20) alkyl, -NR ^k R ^l or R ^m -SiR ⁿ R ^o, and;
_{R 4, R 5, R 10} , R 11 and R ₁₂ independently represent (C1-C20) alkyl, halo (C1-C20) alkyl, (C3-C20) cycloalkyl, (C1-C20) alkyl (C6- (C6-C30) aryl, (C6-C30) aryl, (C1-C20) alkoxy (C6-C30) aryl, ) (C1-C20) alkyl, -NR ^k R ^l or R ^m -SiR ⁿ R ^o, and;
R _6, R _7, R ₈ and R ₉ are each independently hydrogen, (C1-C20) alkyl, halo (C1-C20) alkyl, (C3-C20) cycloalkyl, (C1-C20) alkoxy, (C6- (C 1 -C 20) alkyl, (C 1 -C 20) alkyl, (C 1 -C 20) aryl, (C 1 -C 20) alkyl (C 6 -C 30) aryl, , (C1-C20) alkoxy (C6-C30) aryl, (C6-C30) aryloxy, (C1-C20) alkyl (C6-C30) aryloxy, N- carbazolyl, -NR ^k R ^l or ^m -SiR R ⁿ R ^o or may be connected to an adjacent substituent with a (C 1 -C 5) alkylene to form a ring, and one or more CH ₂ - of said alkylene is selected from -O-, -S- and NR'- Lt; / RTI > may be substituted with a heteroatom, said alkylene may be further substituted with (C1-C20) alkyl;
R 'and R ^k to R ^o are independently of each other (C 1 -C 20) alkyl or (C 6 -C 30) aryl;
X ₁ and X ₂ are independently of each other selected from the group consisting of halogen, (C 1 -C 20) alkyl, (C ₂ -C 20) alkenyl, (C 3 -C 20) cycloalkyl, (C 6 -C 30) aryl, (C 1 -C 20) alkyl, (C 1 -C 20) alkyl ((C 1 -C 20) alkyl (C 6 -C 30) aryl) Anion consisting of up to 60 atoms including N, P, O, S, Si, halogen except hydrogen, (C1-C60) aryloxy, (C1- C20) alkoxy Or a double anion ligand, provided that when either one of X ₁ or X ₂ is a double anionic ligand, the other is ignored. A process for preparing an olefin polymer using a hybrid supported metallocene catalyst according to any one of claims 1 to 11.
14. The method of claim 13,
Wherein the olefin polymer is a homopolymer or copolymer of an alpha olefin.
15. The method of claim 14,
The alpha olefins may be selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, -Methyl-1-butene. ≪ / RTI >
delete